Reflection spectrum Thin films

RAIRS spectra contain absorption band structures related to electronic transitions and vibrations of the bulk, the surface, or adsorbed molecules. In reflectance spectroscopy the ahsorhance is usually determined hy calculating -log(Rs/Ro), where Rs represents the reflectance from the adsorhate-covered substrate and Rq is the reflectance from the bare substrate. For thin films with strong dipole oscillators, the Berre-man effect, which can lead to an additional feature in the reflectance spectrum, must also be considered (Sect. 4.9 Ellipsometry). The frequencies, intensities, full widths at half maximum, and band line-shapes in the absorption spectrum yield information about adsorption states, chemical environment, ordering effects, and vibrational coupling. 

In order to obtain the infrared spectrum of a thin film on a reflecting substrate, a transmission experiment is out of the question since infrared radiation cannot be transmitted through any significant thickness of a reflecting material. Instead,... 

This characteristic of RAIR can be observed experimentally. Fig. 8 shows the transmission spectrum of polydimethylsiloxane (PDMS) while Fig. 9 shows the RAIR spectrum of a thin film of PDMS spin-coated onto a chromium substrate. It can be observed that the bands near 1024 and 1095 cm have similar intensities in the transmission spectra but the band at higher frequencies is clearly much more intense in the RAIR spectrum. This change in relative intensity when PDMS is deposited onto a reflecting substrate is related to optical effects and is not related to orientation effects. 

Observation of absorption bands due to LO phonons in RAIR spectra of thin, silica-like films deposited onto reflecting substrates demonstrates an important difference between RAIR and transmission spectra. Berreman has shown that absorption bands related to transverse optical (TO) phonons are observed in transmission infrared spectra of thin films obtained at normal incidence [17]. However, bands related to LO phonons are observed in transmission spectra of the same films obtained at non-normal incidence and in RAIR spectra. Thus, it is possible for RAIR and transmission spectra of thin films of some materials to appear very different for reasons that are purely optical in nature. For example, when the transmission infrared spectrum of a thin, silica-like film on a KBr disc was obtained at normal incidence, bands due to TO phonons were observed near 1060,790,and450cm [18]. 

The developed sensor was used for ultrathin-film measurement. The reflection spectrum was shifted during the deposition of thin films (e.g., self-assembly of polyelectrolyte layers) onto the sensor end. The reflection between the thin film and the fiber endface was neglected because of their similar refractive indices. As the film increased its thickness, the length of the fiber cavity changed. The amount of change was estimated by the phase shift of the interferogram. The device could also be used as an immunosensor in which the optical thickness changes were used to... 

The thickness of thin film layers separated by uniform, parallel interfaces can be determined from optical interference patterns that result. These measurements can be made from about 400 nm out through the visible spectrum and on into the near-infrared (NIR) region. Since film thickness measurements rely not on the absolnte magnitude of the reflected light, but on the variation of that signal with wavelength, the choice of nnits is less important. Typically %R is used, but in some cases raw intensity is also satisfactory. We will treat thickness determinations in more detail in the applications section of this chapter. 

Atr—ftir can be readily performed on most commercial ftir spectrometers through the use of an attachment for atr spectroscopy. These devices provide ir-transparent internal reflection elements that are typically made of Ge, KRS-5, ZnSe, or ZnS. These internal reflection elements are made of materials that are of extremely high purity to avoid losses from absorption by impurities in these devices. Coupling of a thin film or surface sample to one of these reflection elements is accomplished by pressing the sample against the element while acquiring the spectrum. 

The poly(3, 4 -alkylterthiophene), PTT (2) used in our studies is prepared by FeCl3-mediated oxidative coupling polymerization [39]. PTT with a long alkyl side-chain (R > C6) for example PTT-10 (2, R = n-Ci0H2i) has an ability to self-organize in the solid state as reflected by a bathochromic shift in its UV-visible absorption spectra from solution to thin film (Fig. 4.1a). The solution spectrum of PTT-10 also has a progressive bathochromic shift with concomitant appearance of a longer-... 

For many years, IRRAS has been successfully applied to the study of thin films adsorbates on metal surfaces [36], In the case of monolayers deposited on metal surfaces, an IR external reflection spectrum is obtained by reflecting the incoming radiation from the three-phase ambient-adsorbate-substrate system, measuring the reflected intensity as a function of wavelength, and then ratioing... 

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